Reaction products of dimethylol urea and a halogenated acetamide



' Patented 29, 1946 UNITED STAT OFFICE;

1. ma arm A mocanarnn aca'rauma' Gaetano F. D'Alelio, manna, mu; ma

General Electric Company, a corporation of NewYork NoDrawing.

13 Claims.

This invention relates to the production of new and useful synthetic compositions. More particularly the invention is concerned with novel synthetic resins obtained by reaction of ingredients comprising preformed dimethylol urea and a halogenated acetamide,e. g., mono-, di and 'trichloracetamides, mono-, diand trl-bromacet- 371,394, now Patents, 2,328,424 and 2,328,425, re-

spectively, both of which issued August 31, 1943,

continuation-impart of Application February Serial No. 378,934

and Serial No. 371,395, now Patent 2,377,761, is- T sued June 5, 1945, all. of which applications were filed December 23, 1940, and are assigned to the same assignee as the present invention.

The preparation of resinous materials by eflecting reaction between urea, thiourea or a substituted urea or thiourea containing at least one reactive grouping and an aldehyde, e'. g., formaldehyde, has been known for many years. Such resins and articles produced therefrom are now being made appropriate heat treatment of preformed di-v methylol urea. However, to the best of my knowledge and belief no resins produced by mere heat treatment of preformed dimethylol urea have had the properties necessary to render them of any commercial value. The suggestion also has been made that acetamide be incorporated into a ureaformaldehyde resinous condensation product in order to plasticize the resin. Such plasticized resins and molding compositions made therefrom require the addition of a direct (active) or a latent curing catalyst in order to accelerate their conversion to an insoluble andinfusible state and to render them practically useful in the plastics art.

In my above-identified copending applications I showed that resinous products having particularly valuable properties could be produced by effecting reaction between an aminotriazine, e. g., melamine, and a preformed poly-(N-carbinol) derivative of a urea, e. g., preformed dimethylol urea (Serial No. 371,393, now Patent 2,328,424); also, by eil'ecting reaction between a preformed poly-(N-carbinol) derivative of a urea and a preformed mono or poly- (N-carbinol) derivative of an aminotriazine, e. g., the methylol melamines (Serial No. 371,394,,now Patent 2,328,425); also,

'by eifecting reaction between a urea and a preformednpoly-(N-carbinol) derivative of a urea. I further disclosed in the above-identifled copendin'g applications that various curing reactants, including halogenated acetamides, specifically mono-, diand trl-chloracetamides, when intercondensed. with the above partial reaction products, caused the potentially reactive resinous syrup rapidly to convert to an insoluble, infu'siblee. g., 100 to 200 0.

The present-invention that novel synthetic resins of particular value in the plastics and coating arts can be prepared by eflecting reaction between-ingredients com prising essentially preformed dimethylol urea and a halogenated acetamide. 'The. reaction may be carried out underacid, neutral'or alkaline conditions, at normal or at elevated temperatures, at atmospheric, sub-atmospheric or super-atmospheric pressures, and in the presence or absence of solvents, diluents, fillers, plasticizers, other.

state'when subjected to an elevated temperature,

7 natural or synthetic resins or resin-forming materials. These new resins are characterized by their high resistance to water in cured state as compared'with the ordinary, cured urea-formaldehyde resins. Furthermore, the heat-convertible resinous'syrups and molding compounds prepared therefrom have excellent timeor storagestability, that is, they can be stored for long periods of time without materially advancing toward the insoluble, infusible state. Also. at temperatures of the order of 100 to 180 C. the resins and molding compounds of this invention convert rapidly to the insoluble and infusible or cured weight.

Example 1 Parts Preformed dimethylol urea 120.0 Chloracetamide (monoch1oracetamide) 1.5

Water 120.0

is based on my discovery sistance. v

the water and the resulting solution was heated imder reflux at the boiling temperature of the I mass for 30 Then the chloraoetamide was added and reaction between the chloracetamide and the dimethylol lures, was efiected by heating the components together under reflux for 15 minutes, 'A heat-hardenable resinous syrup.

was obtained. When a small sample of this syrup was heated on a 140 C. hot plate, it cured rapidly to an insoluble, iniusible state.

pound prepared from the resinous syrup of this example exhibited more rapid curing character- A molding (moldable) compound was made by a mixing the syrup produced as described above with 70 parts alpha cellulose in flock form and 0.4 part of a mold lubricant, specifically zinc stearate. The wet compound was dried at 64 C. i'ortwo hours. The dried compound was molded for 5 minutes at 130 C. under a pressure or 2,000 pounds per square inch. The molded piece was well cured throughout and had good water re- Example 2 A resin was prepared as described under Example 1 with the exception that 2 partsvdichloracetamide were usedinstead oi! 1.5 parts monochloracetamide. The resin syrup, when tested on a 140 C. hot plate, cured somewhat more slowly to the insoluble, iniusible state than the correspending product of Example 1.

A molding compound was made as in Example 1. The -wet compound was dried at 64. C. .for 2% hours. Molding the dried compound for '7 minutes at 130 C. and 2,000 pounds per square inch pressure yielded a well-cured molded piece. The compound showed good now characteristics during molding.

- Example 3 I The same procedure was followed in making a resin syrup as set forth under Example 1 with hot plate.

A molding compound, prepared as described under Example 1, was dried at 64 C. for 2% hours. A well-cured molded article that showed good plastic fiow'during molding was obtained by molding the dried compound for '7 minutes at istics than the syrup of Example 2.

Example 5 Parts Preformed dimethylol urea 120.0 Monochloracetamide 1.0 Aqueous ammonia (28% N83) 6.0 Sodium hydroxide in 5 parts water- 0.1 Water 120.0-

All of the above components with the exception of the monochloracetamide were heated together under reflux at the boiling temperature of the mass for 30 minutes. The monochloracetamide was now added and heating under reflux was con-.

tinued for 15 minutes. Testing of a smallsam- I ple of the resulting syrup on a 140 C. hot plate showed that it cured readily to an insoluble, in-

iusible state. A

A molding composition, made as described under Example 1, was dried at 64 C. for 1 hour. Molding the dried compound for 5 minutes at 130 C. and 2,000 pounds per square inch pressure yielded a well-cured molded piece of good appearance.

Example 6 I Parts Preformed dimethylol urea... 120.0 Melamine 42.0 Aqueous ammonia (28% KHz) 6.0 Sodium hydroxide in 5 parts water 0.1 Monochloracetamide e 1.5 Water 160.0

All of the above components with the exception of the monochloracetamide were heated together under reflux at boiling temperature for 30 minutes, after which the monochloracetamide was added and refluxing was continued, for an additional 5 minutes. A small sample of the syrup .was tested for its curing characteristics by heatidly to a hard, infusible resin.

130 C. under 2,000 pounds per square inch pres- The dimethylol urea, ammonia and water were heated together under reflux at the boiling temperature of the mass for 30 minutes. The dichloracetamide was now added and the ammonical solution was heated under reflux ior an additional 15 minutes to, effect reaction between the preformed dimethylol urea and the dichloracetamide. The resulting syrup cured to an insoluble and iniusible resin when a small sample of it was heated on a 140 C. hot plate.

A moldingv compound was made as described under Example 1. The wet compound was dried at 64 C. for 1 hrs. The dried compound was molded at 130 C. under a pressure of 2,000 pounds per square inch for 5 minutes. I A well-cured molded piece was obtained. The molding comsure. r

Example 4 Parts Preformed dimethylol urea 120.0 Dichloracetamide 2.0 I Aqueous ammonia (28% KHz) 6.0

Water 120.0

. A molding compound was made from this syrup as described under'Example 1. The wtcompound was dried for 2 hours at 64C. A well cured molded piece 01' good water resistance was obtained by molding the dried compound for 3 minutes at C. under a pressure 0! 2,00

p unds per square. inch.

" Erampl 7 l V under Example 1, was dried at 64 C. for 2 hours. Molding the dried compound for 5 minutes at 130 C. under a pressure of 2,000 pounds per square inch yielded a well-cured moldedarticle of high resistance to water and of good sur-.

face appearance.

It will be understood, of course, by those skilled in the art that my invention is not limited to the specific components named in the above illustrative examples. Thus, instead of using monochloracetamide (ClCHzCONHz) dichloracetamide (ClzCHCONHi) or trichloracetamide ClaCCONH:

alone or mixed with one another, I may use any v r 2,898,752 other halogenated acetamide, or mixture there oi, e. g., monobromacetamide, dibromacetamide. tribromagetamide, mixtures of brominated acetamidesflnixtures of chlorinated and brominated acetamides, etc. 'I'he choice of the halogenated acetamide is dependent largely upon economic considerations and the particular properties desired in the final product. For example, when light-colored molded articles-are desired the use of the iodo derivatives should be avoided; and when the resinous reaction product is to be used in the production of molding compositions, the fluerinated acetamides preferably are not employed. I prefer to eifect reaction between ingredients comprising, by weight, a preponderant proportion oi preformed dimethylol urea and a minor proportion of a chlorinated acetamide or of a mixture of chlorinated acetamides.

If a condensation catalyst is used to accelerate the condensation reaction between the components, I prefer to use an alkaline or basic condensing agent. Condensation products having excellent storage-stability characteristics can be obtained by causing the condensation reaction totake place in the presence of a condensation catalyst comprising a primary condensation catalyst and a secondary condensation catalyst. As the amount of the primary catalyst, should be a fixed alkali, for instance a carbonate, cyanide or by droxide of an alkali metal (e. g., sodium, potassium, lithium, etc.). Thus, resinous products of exceptional storage stability may be obtained by causing ingredients comprising essentially preformed dimethylol urea and a halogenated acetamide, specifically a chlorinated acetamide, to react in the presence of a condensation catalyst comprising a relatively small amount of ammonia and a lesser but substantial amount of a fixed alkali, for example sodium or potassium hydroxide.

In producing my new compositions of matter comprising a reaction product of ingredients comprising preformed dimethylol urea and a halogenated acetamide, the ratio between the components may be varied as desired or as conditions may require. Usually the halogenated acetamide is used in an amount ranging from 0.001 to 0.25

mol of the halogenated amide for each mol ofpreformed dimethylol urea. The use of a higher ratio of halogenated acetamide to preformed dimethylol urea is not precluded, but no particular advantage, ordinarily accrues from using more halogenated acetamide than required to impart the desired curing characteristics to the heat-convertible resin.

The properties of the fundamental resins oi this invention may be varied widely by introducing other modifying bodies before, during or after effecting condensation between the primary components. Thus, as modifying agents I may use, for instance, monohydric alcohols such as ethyl, propyl, isopropyl, butyl, amyl, etc., alcohols; polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerine, pentaerythritol, etc.; monoand poly-amides, e. g., formamide, acetamide, stearamide, acryloamide, benzamide, toluene sulfonamide, benzene disulfonamidabenzene trisulfonamide, malonic -diamide, itaconic diamide, fumaric diamide, maleic diamide, adipic diamide, phthalamide, urea, thiourea, selenourea, iminourea, substituted ureas, thioureas, selenoureas and iminoureas, numerous examples of which are given in various copending application of mine, for example in my copending application Serial No. 371,395, now Patent 2,377,761 aminotriazines (amidogentriazines), e. g., melamine, ammeline, ammelide, numerous other examples of which are given in various copending applications of mine, for instance in my copending application Serial No. 371,393, now Patent 2,328,424; methylol derivatives of, for example, aminotriazines, monoamides, polyamides other than urea, etc., e. g., the methylol melamines including trimethylol mel amine; amines, e. g., ethylene diamine, aniline, phenylene ,diamine, etc.; phenols, including aminophenols, etc.; ketones; nitriles, e. g., acryl-" succinonitrile, etc.;

aminodiazine, an aminodiazole or an aminotriazine, phenol-aldehyde condensation products. furfural condensation products, modified or unmodified, saturated or unsaturated polyhydric alvcohol-polycarboxylic acid condensation products,

sulfonamide-aldehyde resins, Water-soluble cellulose derivatives, natural gums and resins such as shellac, rosin, etc. polyvinyl compounds such as polyvinyl alcohol, polyvinyl esters, e. g., polyvinyl acetatc, etc., polyvinyl ethers, including the polyvinyl acetals, e. g, polyvinyl formal, etc., polyvinyl ketones, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and various fillers (e. g., wood flour, glass fibers, asbestos, including refibrated asbestos, mineral wool, mica, cloth cuttings, etc.) may be compounded with the resin in accordance with conventional practice to provide molding compositions best fitted to yield molded articles of optimum properties for the particular service application.

The molding compositions of this invention may be molded into a wide variety of shapes under heat or under heat and pressure, more particularly at temperatures of the order of to' 180 C. For optimum results I prefer to use temperatures. ranging from approximately to C'. Molding pressures may be varied considerably, but usuall are within the range of 1,000 to 10,000 pounds per square inch, more particularly from 2,000 to 4,000 or 5,000 pounds per of laminated articles wherein sheetmaterials, l

e. g., paper, cloth, sheet asbestos, etc., are coated and impregnated with the resin, superimposed,

and thereafter united under heat and pressure.

They also may be used in the production of wire or baking enamels, and for binding or cementing together mica flakes to make a laminated mica article. They are particularly useful as fire retardants and sizings for cotton, linen and other cellulosic'materials. They also may be used as impregnants for electrical coils. The cured products have excellent resistance to heat and water and have a high dielectric strength,

What I claim as new and desire to secureby Letters Patent of the United States is: y

1. A composition comprising a product of reaction, under heat, -of ingredients comprising. preformed dimethyloi urea and a halogenated acetamide.

2. A composition comprising an alcohol-modified product of reaction, under heat, of ingredients comprising preformed dimethylol urea and a halogenated acetamide.

3. A heat-curable composition comprising the product of reaction, under heat, of ingredients comprising preformed dimethylol urea and a.

chlorinated acetamide.

4. A product comprising the cured composi- 7 tion of claim 3.

5. A resinous composition obtained by reaction, under heat and in the presence of an alkaline substance, of ingredients comprising a chlorinated acetamide and preformed dimethylol urea in the ratio of from 0.001 to 0.25 mol of the former to 1 m0] of the latter.

" not of reaction, under heat, of ingredients comprising preformed dimethylol urea and a mix! ture of chlorinated acetamides.

8, A resinous composition obtained by reaction, under heat, of ingredients comprising preformed dimethylol urea and monochloracetamide.

9. A resinous composition obtained by reaction,

under heat, of ingredients comprising preformed dimethylol urea and dichloracetamide.

10. A composition comprising (1) a resinous product of reaction, under heat, of ingredients comprising preformed. dimethylol urea and a chlorinated acetamide, and (2) 9i urea-formaldehyde resinous condensation product.

11. A heat-hardenable molding composition comprising a. celluloslc filler and a heat-curable product of reaction, under heat, of ingredients comprising preformed dimethyloi urea and a chlorinated acetamide.

12; An article of manufacture comprising the heat-hardened molding composition of claim 11.

13. The method of preparing new compositions of matter which comprises effecting reaction under heat between ingredients comprising preformed dimethylol urea and a halogenated acetamide.

GAETANO F. D'ALELIQ' 

